CN103985900A - Modified polymer electrolyte, preparing method of modified polymer electrolyte and application of modified polymer electrolyte to lithium battery - Google Patents
Modified polymer electrolyte, preparing method of modified polymer electrolyte and application of modified polymer electrolyte to lithium battery Download PDFInfo
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- CN103985900A CN103985900A CN201410171454.5A CN201410171454A CN103985900A CN 103985900 A CN103985900 A CN 103985900A CN 201410171454 A CN201410171454 A CN 201410171454A CN 103985900 A CN103985900 A CN 103985900A
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- polymer electrolyte
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- electrolyte
- lithium
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- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title abstract description 9
- 229910052744 lithium Inorganic materials 0.000 title abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 42
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 19
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 19
- 239000003792 electrolyte Substances 0.000 claims abstract description 13
- 239000002608 ionic liquid Substances 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims description 57
- 229910001416 lithium ion Inorganic materials 0.000 claims description 48
- 239000002105 nanoparticle Substances 0.000 claims description 32
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 25
- 238000002360 preparation method Methods 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 17
- -1 tetrafluoroborate Chemical compound 0.000 claims description 16
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 10
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011159 matrix material Substances 0.000 claims description 10
- 239000005543 nano-size silicon particle Substances 0.000 claims description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 8
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 8
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 4
- 239000007822 coupling agent Substances 0.000 claims description 4
- 150000002466 imines Chemical class 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- 238000002203 pretreatment Methods 0.000 claims description 4
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- TYOCDPIZUIQUSO-UHFFFAOYSA-N 1-butyl-2,3-dimethyl-2h-imidazole Chemical compound CCCCN1C=CN(C)C1C TYOCDPIZUIQUSO-UHFFFAOYSA-N 0.000 claims description 2
- CDXLWOUTFCMPDM-UHFFFAOYSA-N 1-butyl-4-methyl-2h-pyridine Chemical compound CCCCN1CC=C(C)C=C1 CDXLWOUTFCMPDM-UHFFFAOYSA-N 0.000 claims description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 2
- 238000006424 Flood reaction Methods 0.000 claims description 2
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 2
- 229910013131 LiN Inorganic materials 0.000 claims description 2
- 229910012513 LiSbF 6 Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 claims description 2
- NDZWKTKXYOWZML-UHFFFAOYSA-N trilithium;difluoro oxalate;borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FOC(=O)C(=O)OF NDZWKTKXYOWZML-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 239000002245 particle Substances 0.000 abstract description 20
- 239000011244 liquid electrolyte Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 230000009477 glass transition Effects 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 229920000307 polymer substrate Polymers 0.000 abstract 2
- 238000005470 impregnation Methods 0.000 abstract 1
- 238000001291 vacuum drying Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 32
- 239000000243 solution Substances 0.000 description 24
- 230000004048 modification Effects 0.000 description 19
- 238000012986 modification Methods 0.000 description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- 239000002904 solvent Substances 0.000 description 14
- 229910052782 aluminium Inorganic materials 0.000 description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 13
- 239000002131 composite material Substances 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 239000004411 aluminium Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 229920006280 packaging film Polymers 0.000 description 12
- 239000012785 packaging film Substances 0.000 description 12
- 229920003023 plastic Polymers 0.000 description 12
- 239000004033 plastic Substances 0.000 description 12
- 229940017219 methyl propionate Drugs 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 description 10
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 10
- 230000004913 activation Effects 0.000 description 8
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 8
- 229920001519 homopolymer Polymers 0.000 description 8
- 238000007873 sieving Methods 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229910013075 LiBF Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910013872 LiPF Inorganic materials 0.000 description 4
- 101150058243 Lipf gene Proteins 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 3
- 239000006183 anode active material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910010093 LiAlO Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 208000002925 dental caries Diseases 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 229940043237 diethanolamine Drugs 0.000 description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 2
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 1
- IMIMVUJTMYKZAB-UHFFFAOYSA-N CC(C)C(N)=O.CC(C)C(N)=O.CC(C)C(N)=O.CC(C)C(N)=O.CC(C)C(N)=O.CC(C)C(N)=O.N.N Chemical compound CC(C)C(N)=O.CC(C)C(N)=O.CC(C)C(N)=O.CC(C)C(N)=O.CC(C)C(N)=O.CC(C)C(N)=O.N.N IMIMVUJTMYKZAB-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 102000011759 adducin Human genes 0.000 description 1
- 108010076723 adducin Proteins 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000002194 amorphous carbon material Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DISYGAAFCMVRKW-UHFFFAOYSA-N butyl ethyl carbonate Chemical compound CCCCOC(=O)OCC DISYGAAFCMVRKW-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- LEGITHRSIRNTQV-UHFFFAOYSA-N carbonic acid;3,3,3-trifluoroprop-1-ene Chemical compound OC(O)=O.FC(F)(F)C=C LEGITHRSIRNTQV-UHFFFAOYSA-N 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- JMPVESVJOFYWTB-UHFFFAOYSA-N dipropan-2-yl carbonate Chemical compound CC(C)OC(=O)OC(C)C JMPVESVJOFYWTB-UHFFFAOYSA-N 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000011366 tin-based material Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Conductive Materials (AREA)
Abstract
The invention relates to modified polymer electrolyte, a preparing method of the modified polymer electrolyte and application of the modified polymer electrolyte to a lithium battery. The modified polymer electrolyte comprises all-solid-state polymer electrolyte or gel-state polymer electrolyte, wherein the all-solid-state polymer electrolyte is prepared according to a preparing method that hyperbranched monomers, inorganic nanometer particles, polymer substrates and lithium salts jointly take reaction; the gel-state polymer electrolyte is prepared according to a preparing method that the hyperbranched monomers, the inorganic nanometer particles and the polymer substrates jointly take reaction, and electrolyte/ionic liquid and lithium salt impregnation is carried out after mold film forming and vacuum drying. The modified polymer electrolyte has the advantages that the glass transition temperature and the crystallinity of the polymer electrolyte can be reduced, and the compatibility with electrodes and other materials is improved; the problems that electrolyte leakage of liquid electrolyte easily occurs, and the leakage current is heavy can be solved; the application range of the polymer electrolyte to the lithium battery is wider.
Description
Technical field
The invention belongs to lithium ion battery field, be specifically related to hyperbranched nanometer particle-modified polymer dielectric, its preparation method and the application in polymer Li-ion battery thereof.
Background technology
Along with the development of World Economics, people are increasing to the demand of the energy, require also more and more higher, under the background of human survival and development in Global climate change profound influence simultaneously, taking low energy consumption, low emission, low pollution as basic low carbon development, day by day become global tracking focus and world trends.Lithium ion battery is a main direction of new forms of energy development, and lithium ion battery is not only widely used in such as mobile phone, notebook, panel computer etc. in daily life electrical equipment, also in electric automobile, hybrid vehicle, makes first appearance.
1985, people adopted the material with carbon element substituted metal lithium of porous as the negative material of lithium rechargeable batteries, have tentatively proposed to possess the lithium ion battery (LIB) of real use value.What lithium ion battery now adopted is liquid electrolyte, it comprises lithium salts and solvent, in use still exist lithium ion can form in negative pole deposition the possibility of tree-shaped crystalline substance, it may puncture barrier film, cause internal short-circuit of battery, and the danger of electrolyte leakage, there is potential potential safety hazard.Armand adopted pure solid electrolyte to replace liquid electrolyte afterwards, prepare lighium polymer electrolytic cell (Li-SPE battery), because this battery just has higher conductivity at 80 DEG C, therefore it is only for the research for stand-by power supply and electrokinetic cell.Within 1993, U.S. Bellcore research worker adopts advanced process technology successfully polymer dielectric to be incorporated in liquid lithium ionic cell system, prepares the lithium ion polymer battery (LIPB) of stable performance.It is high that lithium ion polymer battery has specific energy, can be processed into the advantages such as arbitrary shape, meets the more and more microminiaturized needs of current compact electric apparatus.
Inorganic nano-particle refers to inorganic particulate between diameter 1～100nm (as nano silicon, titanium dioxide, aluminium oxide, magnesium oxide, iron oxide etc.), nano particle has some strange physicochemical characteristicss, its surface area accounts for very large proportion, and both amorphous layers without short-range order without long-range order of surface atom.Can think that the state of nanoparticle surface atom more approaches gaseous state, and the atom of inside particles may be orderly arrangement.Nano particle has bulk effect, skin effect, quantum size effect, macro quanta tunnel effect.Dissaving polymer has low viscosity, and chain itself is without being wound around; Crystal property is poor; There are the reactive functional groups of One's name is legion and molecular memory in design features such as cavitys.Due to highly branched topological structure, make super branched molecule in three dimensions, have almost spherical structure, its size, between a few nanometer to tens nanometers, is generally also typical nano material simultaneously.
Dissaving polymer is the highly branched molecular structure of 3 D stereo, has lower melt viscosity and lower intermolecular cross-linking, and its shape end is connected with a large amount of active function groups, contributes to further to participate in chemical reaction.Grafted by super branched polymer can greatly be weakened to the reunion between nano particle to inorganic nano-particle, increase the dissolubility of nano particle and reduce viscosity, can prepare the compound that has nano particle and dissaving polymer advantage concurrently, meet the growing needs of industry.
Summary of the invention
The object of the invention is to overcome prior art above shortcomings, a kind of modified polymer electrolyte is provided.
Another object of the present invention is to provide the preparation method of above-mentioned modified polymer electrolyte.
Another object of the present invention is to provide the application of above-mentioned modified polymer electrolyte in polymer Li-ion battery.
For achieving the above object, the present invention adopts following technical scheme:
A kind of modified polymer electrolyte, described modified polymer electrolyte comprises full solid state polymer electrolyte or gel polymer electrolyte;
Wherein, the preparation method of described full solid state polymer electrolyte is for to react hyperbranched monomer, inorganic nano-particle, polymeric matrix and lithium salts one;
The preparation method of described gel polymer electrolyte is for to react hyperbranched monomer, inorganic nano-particle and polymeric matrix one, floods electrolyte/ionic liquid and lithium salts is prepared gained after mould film forming, vacuumize.
Preferably, the concrete steps that described hyperbranched monomer, inorganic nano-particle, polymeric matrix and lithium salts one react are: first inorganic nano-particle and hyperbranched monomer are generated to hyperbranched modified inorganic nano-particle.
Preferably, described inorganic nano-particle also comprises pre-treatment step, and described pre-treatment step is for to process inorganic nano-particle with coupling agent.
Preferably, the diameter of described inorganic nano-particle is 50～200nm.
Preferably, described inorganic nano-particle is nano silicon, titanium dioxide, aluminium oxide, iron oxide, magnesium oxide, lithium metaaluminate, one or more in layered double-hydroxide.
Preferably, described coupling agent is gamma-aminopropyl-triethoxy-silane, γ-methacryloxypropyl trimethoxy silane, 3-isocyanates methylene-3, one or more in 5,5-3-methyl cyclohexanol based isocyanate.
Preferably, described lithium salts is LiClO
4, LiPF
6, LiCF
3sO
3, LiBF
4, LiAsF
6, LiSbF
6, LiN (CF
3sO
2)
2, LiCF
3cF
2sO
3, one or more in difluoro (oxalic acid) lithium borate or (the third dioxalic acid) lithium borate; Described polymeric matrix is one or more in polyethers system, polyacrylonitrile, polymethyl methacrylate, Kynoar; Described ionic liquid is 3-methyl isophthalic acid-ethyl imidazol(e) tetrafluoroborate, N-methyl-N-propyl pyrrole two (trimethyl fluoride sulfonyl) imines, 1-butyl-4-picoline two (trimethyl fluoride sulfonyl) imines, one or more in 1,2-dimethyl-3-n-butyl imidazole.
Further preferably, described lithium salts is LiPF
6, LiCF
3sO
3or LiBF
4, described polymeric matrix is that polyethylene glycol oxide, described ionic liquid are 3-methyl isophthalic acid-ethyl imidazol(e) tetrafluoroborate.
The application of above-mentioned modified polymer electrolyte in polymer Li-ion battery.
Further preferably, described polymer Li-ion battery comprises all solid state lithium ion polymer battery and gel polymer battery.
The preparation method of described polymer Li-ion battery is as follows:
In the time preparing all solid state lithium ion polymer battery, first all solid state modified polymer electrolyte is processed into needed shape, then itself and anodal and negative pole is stacked togather, compress, be sealed in button cell or aluminium plastic composite packaging film, be assembled into all solid state lithium ion polymer battery;
In the time preparing gel-state lithium ion polymer battery, first hyperbranched nano particle and polymer dielectric are prepared to composite Nano polymer film, then after soaking, lithium salt solution obtains gel polymer electrolyte, again positive pole, gel polymer electrolyte and negative pole are stacked togather, compress, be sealed in button cell or aluminium plastic composite packaging film, be assembled into polymer Li-ion battery.
Wherein, battery anode active material comprises cobalt-lithium oxide (LiCoO
2), nickel oxide lithium (LiNiO
2), manganese oxide lithium (LiMn
2o
4) and the oxide of vanadium; Positive electrode active materials, electric conducting material, adhesive and nonaqueous solvents are mixed to prepare anode active material composition, then this anode active material composition is directly coated on aluminum current collector dry to prepare positive plate.
Preferably, described nonaqueous solvents is vinyl carbonate (EC), propylene carbonate (PC), butylene carbonic ester (BC), 1,2-dimethyl vinyl carbonate (1,2-BC), ethyl butyl carbonate (BEC), carbonic acid first butyl ester (BMC), diethyl carbonate (DEC), dimethyl carbonate (DMC), trifluoromethyl ethylene carbonate (CF
3-EC), one or more in carbonic acid di-n-propyl ester (DPC) and carbonic acid diisopropyl ester (DIPC).
Further preferably, described nonaqueous solvents is vinyl carbonate (EC) and dimethyl carbonate (DMC).
Battery cathode active material is graphitized carbon material, amorphous carbon material, nitride, silica-base material, tin-based material, one or more in novel alloy and nano-oxide; The preparation of similar positive plate, mixes to prepare negative electrode active material feed composition by negative active core-shell material, electric conducting material, adhesive and nonaqueous solvents, then this negative electrode active material feed composition is directly coated on copper collector to prepare negative plate.
In the time preparing polymer Li-ion battery, guarantee polymer dielectric and battery plus-negative plate material to compress, making has good contact between both positive and negative polarity and polymer dielectric, and wherein containing air with bubble; All under inert gas shielding, carry out at all operations of preparing polymer Li-ion battery.
In the present invention, adopt hyperbranched nano particle to carry out hyperbranched processing to polymer dielectric, due to hyperbranched nano particle have low viscosity, chain itself without being wound around, feature that crystal property is poor have the reactive functional groups of One's name is legion, molecular memory can promote to reduce the glass transition temperature of polymer dielectric in design features such as cavitys, the position that provides lithium ion to carry out complexing and solvation, and be conducive to the migration of lithium ion.
Compared with prior art, the present invention has following beneficial effect: reduce glass transition temperature and the degree of crystallinity of polymer dielectric, the compatibility of raising and electrode and other materials; There is certain mechanical strength and good processing characteristics; Can solve liquid electrolyte electrolyte leakage and the large problem of leakage current easily occur; Be easy to miniaturization, can be processed into arbitrary shape, and can prepare large-area ultrathin film, meet the requirement of battery miniaturization, flexibility; The present invention makes polymer dielectric more extensive in the application aspect of lithium battery.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.These embodiment describe typical case of the present invention, but the invention is not restricted to this.
In all embodiment provided by the invention, the raw material that provide all can obtain from market buying.
The preliminary treatment of embodiment 1 inorganic nano-particle
Take a certain amount of nanometer SiO
2be placed in 500mL tetra-neck flasks, m (KH550): m (SiO with KH550
2)=2: 1,95% ethanol is solvent, and ultrasonic dispersion 30min moves in oil bath, and mechanical agitation 12h at 100 DEG C, obtains surface and introduces amino nanometer SiO
2(SiO
2-KH550), then add 2 times to the MMA of KH550 molar equivalent, add 0.5wt% caustic alcohol, keeping temperature is 40 DEG C of reaction 48h.Obtain the nano silicon (SiO of KH550 and MMA modification
2-KH550-MMA).
The preparation of embodiment 2 hyperbranched monomers
Taking 20.0g adopts methyl methacrylate (MMA) and 20.0g diethanol amine (DEA) to join in the four-necked bottle that thermometer, blender, condenser pipe are housed, add 0.5wt% caustic alcohol, keeping temperature is 40 DEG C of reactions one week, then in 60 DEG C of water-baths, revolve and steam the hyperbranched monomer of removing unreacted reactant: N, N-dihydroxy ethyl-3-aminomethyl methyl propionate.
The preparation of embodiment 3 polymer Li-ion batteries
(1) the hyperbranched monomer N that modified manometer silicon dioxide (SiO2-KH550-MMA) ethanolic solution that the embodiment 1 that is 15% by mass fraction obtains and mass fraction 85% embodiment 2 obtain; N-dihydroxy ethyl-3-aminomethyl methyl propionate is placed in four neck flasks, under nitrogen protection, stirs.
(2) after the nano-silicon dioxide particle and hyperbranched monomer of the modification in abundant whipping step (1), add catalyst p-methyl benzenesulfonic acid by the amount of hyperbranched monomer 0.5wt%, heating vacuumizes stirring reaction 2h;
(3) get products therefrom in (2) by mass fraction 20%, then add the acetonitrile solution of 70% polyethylene glycol oxide (MW=100000～8000000), continue heating and vacuumize stirring reaction 12h, finally add 10% lithium salts LiClO
4, after stirring, product being poured in polytetrafluoroethylene mould, vacuumize, obtains all solid state modified polymer electrolyte;
(4) positive pole, all solid state modified polymer electrolyte and negative pole are stacked togather, compress, be sealed in button cell or aluminium plastic composite packaging film, be assembled into full solid state polymer lithium ion battery.
The preparation of embodiment 4 polymer Li-ion batteries
(1) press the method preliminary treatment nano titanium oxide (TiO of embodiment 1
2) and the method for embodiment 2 prepare hyperbranched monomer, then by the modified nano-titanium dioxide (TiO of mass fraction 7.5%
2) ethanolic solution and the hyperbranched monomer N of mass fraction 92.5%, N-dihydroxy ethyl-3-aminomethyl methyl propionate is placed in four neck flasks, under nitrogen protection, stirs.
(2) after the modified nano-titanium dioxide particle and hyperbranched monomer in abundant whipping step (1), add catalyst p-methyl benzenesulfonic acid by the amount of hyperbranched monomer 0.5wt%, heating vacuumizes stirring reaction 2h;
(3) get by mass fraction 20% acetonitrile solution that products therefrom in (2) then adds 60% polyethylene glycol oxide (MW=100000～8000000), continue heating and vacuumize stirring reaction 12h, finally add 20% lithium salts LiCF
3sO
3, after stirring, product being poured in polytetrafluoroethylene mould, vacuumize, obtains all solid state modified polymer electrolyte;
(3) positive pole, all solid state modified polymer electrolyte and negative pole are stacked togather, compress, be sealed in button cell or aluminium plastic composite packaging film, be assembled into full solid state polymer lithium ion battery.
The preparation of embodiment 5 polymer Li-ion batteries
(1) the hyperbranched monomer N of the KH550 that the embodiment 1 that is 15% by mass fraction obtains and the nano silicon ethanolic solution of MMA modification and mass fraction 85%, N-dihydroxy ethyl-3-aminomethyl methyl propionate is placed in four neck flasks, add catalyst p-methyl benzenesulfonic acid by the amount of hyperbranched monomer 0.5wt%, after stirring, heating vacuumizes stirring reaction 12h.Product is placed in to apparatus,Soxhlet's, makees solvent with acetone, 80 DEG C of Soxhlet extracting 48h, remove the homopolymers of not grafting, and sieving for standby is ground in vacuumize, obtains the nano-silicon dioxide particle of hyperbranched modification.
(2) get ultrasonic being dispersed in acetonitrile of nano-silicon dioxide particle of the hyperbranched modification obtaining in (1) by mass fraction 0.1%, add the polyethylene glycol oxide (MW=100000～8000000) of 10% lithium salts and 89.9%, after fully stirring, be poured on film forming in polytetrafluoroethylene mould, vacuumize obtains all solid state modified polymer electrolyte;
(3) positive pole, all solid state modified polymer electrolyte and negative pole are stacked togather, be sealed in button cell or aluminium plastic composite packaging film, compress, be assembled into full solid state polymer lithium ion battery.
The preparation of embodiment 6 polymer Li-ion batteries
(1) press the method preliminary treatment nano aluminium oxide (Al of embodiment 1
2o
3) and the method for embodiment 2 prepare hyperbranched monomer, then by the hyperbranched monomer N of the modified nano-alumina ethanolic solution of mass fraction 10% and mass fraction 90%, N-dihydroxy ethyl-3-aminomethyl methyl propionate is placed in four neck flasks, add catalyst p-methyl benzenesulfonic acid by the amount of hyperbranched monomer 0.5wt%, after stirring, heating vacuumizes stirring reaction 12h.Product is placed in to apparatus,Soxhlet's, makees solvent with acetone, 80 DEG C of Soxhlet extracting 48h, remove the homopolymers of not grafting, and sieving for standby is ground in vacuumize, obtains the nano alumina particles of hyperbranched modification.
(2) press the nano aluminium oxide (Al of the hyperbranched modification of mass fraction 0.2%
2o
3) particle is ultrasonic is dispersed in acetonitrile, adds 99.8% polyethylene glycol oxide (MW=100000～8000000), fully after stirring reaction in polytetrafluoroethylene mould film forming, the mixed solution 1M LiPF that dipping absorption is made up of electrolyte and lithium salts after vacuumize
6+ EC:DMC(1:1) to activate, then take out, blot the electrolyte of remained on surface with filter paper, obtain gel polymer electrolyte;
(3) again positive pole, gel polymer electrolyte and negative pole are stacked togather, compress, be sealed in button cell or aluminium plastic composite packaging film, be assembled into gel polymer lithium ion battery.
The preparation of embodiment 7 polymer Li-ion batteries
(1) press the method preliminary treatment nano-sized iron oxide (Fe of embodiment 1
2o
3) and the method for embodiment 2 prepare hyperbranched monomer, then by the hyperbranched monomer N of the modified Nano iron oxide ethanolic solution of mass fraction 5% and mass fraction 95%, N-dihydroxy ethyl-3-aminomethyl methyl propionate is placed in four neck flasks, add catalyst p-methyl benzenesulfonic acid by the amount of hyperbranched monomer 0.5wt%, after stirring, heating vacuumizes stirring reaction 12h.Product is placed in to apparatus,Soxhlet's, makees solvent with acetone, 80 DEG C of Soxhlet extracting 48h, remove the homopolymers of not grafting, and sieving for standby is ground in vacuumize, obtains the nano oxidized iron particle of hyperbranched modification.
(2) be dispersed in acetonitrile ultrasonic the nano oxidized iron particle of the hyperbranched modification of mass fraction 0.5%, add 99.5% polyethylene glycol oxide (MW=100000～8000000), fully stirring all should after in polytetrafluoroethylene mould film forming, the mixed solution 1M LiBF that dipping absorption is made up of ionic liquid and lithium salts after vacuumize
4/ EMIBF
4with activation, then take out, blot the liquid electrolyte solution of remained on surface with filter paper, obtain gel polymer electrolyte;
(3) again positive pole, gel polymer electrolyte and negative pole are stacked togather, compress, be sealed in button cell or aluminium plastic composite packaging film, be assembled into gel polymer lithium ion battery.
The preparation of embodiment 8 polymer Li-ion batteries
(1) press the method preliminary treatment nanometer lithium metaaluminate (LiAlO of embodiment 1
2) and the method for embodiment 2 prepare hyperbranched monomer, then by the hyperbranched monomer N of the nanometer lithium metaaluminate ethanolic solution of mass fraction 5% and mass fraction 95%, N-dihydroxy ethyl-3-aminomethyl methyl propionate is placed in four neck flasks, add catalyst p-methyl benzenesulfonic acid by the amount of hyperbranched monomer 0.5wt%, after stirring, heating vacuumizes stirring reaction 12h.Product is placed in to apparatus,Soxhlet's, makees solvent with acetone, 80 DEG C of Soxhlet extracting 48h, remove the homopolymers of not grafting, and sieving for standby is ground in vacuumize, obtains the nanometer lithium metaaluminate particle of hyperbranched modification.
(2) be dispersed in dimethyl formamide (DMF) ultrasonic the nanometer lithium metaaluminate particle of the hyperbranched modification of mass fraction 1%, add 99% polymethyl methacrylate (PMMA), fully after stirring reaction in polytetrafluoroethylene mould film forming;
(3) LiPF of compound concentration 1.0M
6/ EC:DMC(mass ratio 1:1) solution, the polymethyl methacrylate film after vacuumize is placed in to above-mentioned solution and soaks 1h with activation, dipping absorption LiPF
6/ EC:DMC(mass ratio 1:1) solution with activation, then take out the electrolyte that blots remained on surface with filter paper, obtain gel polymer electrolyte;
(4) again positive pole, gel polymer electrolyte and negative pole are stacked togather, compress, be sealed in button cell or aluminium plastic composite packaging film, be assembled into gel polymer lithium ion battery.
The preparation of embodiment 9 polymer Li-ion batteries
(1) press the method preliminary treatment nanometer lithium metaaluminate (LiAlO of embodiment 1
2) and the method for embodiment 2 prepare hyperbranched monomer, then by the hyperbranched monomer N of the nanometer lithium metaaluminate ethanolic solution of mass fraction 7.5% and mass fraction 92.5%, N-dihydroxy ethyl-3-aminomethyl methyl propionate is placed in four neck flasks, add catalyst p-methyl benzenesulfonic acid by the amount of hyperbranched monomer 0.5wt%, after stirring, heating vacuumizes stirring reaction 12h.Product is placed in to apparatus,Soxhlet's, makees solvent with acetone, 80 DEG C of Soxhlet extracting 48h, remove the homopolymers of not grafting, and sieving for standby is ground in vacuumize, obtains the nanometer lithium metaaluminate particle of hyperbranched modification.
(2) be dispersed in dimethyl formamide (DMF) ultrasonic the nanometer lithium metaaluminate particle of the hyperbranched modification of mass fraction 2%, add 98% polymethyl methacrylate (PMMA), fully after stirring reaction in polytetrafluoroethylene mould film forming;
(3) LiBF of compound concentration 1.0M
4/ EMIBF
4solution, is placed in the polymethyl methacrylate film after vacuumize the LiBF of 1.0M
4/ EMIBF
4in solution, soak 1h with activation, then take out the electrolyte that blots remained on surface with filter paper, obtain gel polymer electrolyte;
(4) again positive pole, gel polymer electrolyte and negative pole are stacked togather, compress, be sealed in button cell or aluminium plastic composite packaging film, be assembled into gel polymer lithium ion battery.
The preparation of embodiment 10 polymer Li-ion batteries
(1) press the method preliminary treatment stratiform double-hydroxide Mg of embodiment 1
2al (OH)
6prepare hyperbranched monomer with the method for embodiment 2, then the hyperbranched monomer N nano double hydroxide ethanolic solution of mass fraction 5% and mass fraction 95% embodiment 2 being obtained, N-dihydroxy ethyl-3-aminomethyl methyl propionate is placed in four neck flasks, add catalyst p-methyl benzenesulfonic acid by the amount of hyperbranched monomer 0.5wt%, after stirring, heating vacuumizes stirring reaction 12h.Product is placed in to apparatus,Soxhlet's, makees solvent with acetone, 80 DEG C of Soxhlet extracting 48h, remove the homopolymers of not grafting, and sieving for standby is ground in vacuumize, obtains the nano double hydroxide particle of hyperbranched modification.
(2) be dispersed in 1-METHYLPYRROLIDONE in (NMP) ultrasonic the nano double hydroxide particle of the hyperbranched modification of mass fraction 5%, add 95% Kynoar (PVDF), fully stir and be all poured on afterwards film forming in polytetrafluoroethylene mould;
(3) LiPF of compound concentration 1.0M
6/ EC:DMC solution, is placed in above-mentioned solution by the polyvinylidene difluoride film after vacuumize and soaks 4h with activation, dipping absorption LiPF
6/ EC:DMC solution, with activation, then takes out the liquid electrolyte solution that blots remained on surface with filter paper, obtains gel polymer electrolyte;
(4) again positive pole, gel polymer electrolyte and negative pole are stacked togather, compress, be sealed in button cell or aluminium plastic composite packaging film, be assembled into gel polymer lithium ion battery.
The preparation of embodiment 11 polymer Li-ion batteries
(1) press the method preliminary treatment stratiform double-hydroxide Mg of embodiment 1
2al (OH)
6prepare hyperbranched monomer with the method for embodiment 2, then by the hyperbranched monomer N of the nano layered double hydroxides ethanolic solution of mass fraction 10% and mass fraction 90%, N-dihydroxy ethyl-3-aminomethyl methyl propionate is placed in four neck flasks, add catalyst p-methyl benzenesulfonic acid by the amount of hyperbranched monomer 0.5wt%, after stirring, heating vacuumizes stirring reaction 12h.Product is placed in to apparatus,Soxhlet's, makees solvent with acetone, 80 DEG C of Soxhlet extracting 48h, remove the homopolymers of not grafting, and sieving for standby is ground in vacuumize, obtains the nano layered double hydroxides particle of hyperbranched modification.
(2) be dispersed in 1-METHYLPYRROLIDONE in (NMP) ultrasonic the nano layered double hydroxides particle of the hyperbranched modification of mass fraction 10%, add 90% polyacrylonitrile (PAN), fully stir and be all poured on afterwards film forming in polytetrafluoroethylene mould;
(3) LiBF of compound concentration 1.0M
4/ EMIBF
4solution, is placed in LiBF by the polyacrylonitrile film after vacuumize then
4/ EMIBF
4in solution, soak 1h with activation, then take out the electrolyte that blots remained on surface with filter paper, obtain gel polymer electrolyte;
(4) again positive pole, gel polymer electrolyte and negative pole are stacked togather, compress, be sealed in button cell or aluminium plastic composite packaging film, be assembled into gel polymer lithium ion battery.
The preparation of embodiment 12 polymer Li-ion batteries
(1) prepare hyperbranched monomer by the method preliminary treatment nano magnesia (MgO) of embodiment 1 and the method for embodiment 2, then quality is divided to 15% nano magnesia ethanolic solution and the hyperbranched monomer N of mass fraction 85% embodiment 2, N-dihydroxy ethyl-3-aminomethyl methyl propionate is placed in four neck flasks, add catalyst p-methyl benzenesulfonic acid by the amount of hyperbranched monomer 0.5wt%, after stirring, heating vacuumizes stirring reaction 12h.Product is placed in to apparatus,Soxhlet's, makees solvent with acetone, 80 DEG C of Soxhlet extracting 48h, remove the homopolymers of not grafting, and sieving for standby is ground in vacuumize, obtains the nano oxidized magnesium particle of hyperbranched modification.
(2) be dispersed in nitrogen nitrogen dimethylacetylamide (DMAC) ultrasonic the nano particle of the hyperbranched modification of mass fraction 15%, add 85% polyacrylonitrile (PAN), fully stir and be all poured on afterwards film forming in polytetrafluoroethylene mould;
(3) LiPF of compound concentration 1.0M
6/ EC:DMC(mass ratio 1:1) solution, polyacrylonitrile film after vacuumize is placed in to above-mentioned solution and soaks 1h with activation, then take out the electrolyte that blots remained on surface with filter paper, obtain gel polymer electrolyte;
(4) again positive pole, gel polymer electrolyte and negative pole are stacked togather, compress, be sealed in button cell or aluminium plastic composite packaging film, be assembled into gel polymer lithium ion battery.
The performance test of the polymer Li-ion battery of embodiment 3～12 preparations is in table 1.
Table 1
As shown in Table 1, polymer Li-ion battery prepared by the present invention has lower glass transition temperature and degree of crystallinity, and the compatibility of electrode and other materials improves; And there is certain mechanical strength and good processing characteristics; Can solve liquid electrolyte electrolyte leakage and the large problem of leakage current easily occur; Be easy to miniaturization, can be processed into arbitrary shape, and can prepare large-area ultrathin film, meet the requirement of battery miniaturization, flexibility; The present invention makes polymer dielectric more extensive in the application aspect of lithium battery.
Claims (10)
1. a modified polymer electrolyte, is characterized in that, described modified polymer electrolyte comprises full solid state polymer electrolyte or gel polymer electrolyte;
Wherein, the preparation method of described full solid state polymer electrolyte is for to react hyperbranched monomer, inorganic nano-particle, polymeric matrix and lithium salts one;
The preparation method of described gel polymer electrolyte is for to react hyperbranched monomer, inorganic nano-particle and polymeric matrix one, floods electrolyte/ionic liquid and lithium salts is prepared gained after mould film forming, vacuumize.
2. modified polymer electrolyte according to claim 1, it is characterized in that, the concrete steps that described hyperbranched monomer, inorganic nano-particle, polymeric matrix and lithium salts one react are: first inorganic nano-particle and hyperbranched monomer are generated to hyperbranched modified inorganic nano-particle.
3. modified polymer electrolyte according to claim 1, is characterized in that, described inorganic nano-particle also comprises pre-treatment step, and described pre-treatment step is for to process inorganic nano-particle with coupling agent.
4. according to the modified polymer electrolyte described in any claim of claims 1 to 3, it is characterized in that, the diameter of described inorganic nano-particle is 50～200nm.
5. according to the modified polymer electrolyte described in any claim of claims 1 to 3, it is characterized in that, described inorganic nano-particle is nano silicon, titanium dioxide, aluminium oxide, iron oxide, magnesium oxide, lithium metaaluminate, one or more in layered double-hydroxide.
6. modified polymer electrolyte according to claim 3, it is characterized in that, described coupling agent is gamma-aminopropyl-triethoxy-silane, γ-methacryloxypropyl trimethoxy silane, 3-isocyanates methylene-3, one or more in 5,5-3-methyl cyclohexanol based isocyanate.
7. according to the modified polymer electrolyte described in any claim of claims 1 to 3, it is characterized in that, described lithium salts is LiClO
4, LiPF
6, LiCF
3sO
3, LiBF
4, LiAsF
6, LiSbF
6, LiN (CF
3sO
2)
2, LiCF
3cF
2sO
3, one or more in difluoro (oxalic acid) lithium borate or (the third dioxalic acid) lithium borate; Described polymeric matrix is one or more in polyethers system, polyacrylonitrile, polymethyl methacrylate, Kynoar; Described ionic liquid is 3-methyl isophthalic acid-ethyl imidazol(e) tetrafluoroborate, N-methyl-N-propyl pyrrole two (trimethyl fluoride sulfonyl) imines, 1-butyl-4-picoline two (trimethyl fluoride sulfonyl) imines, one or more in 1,2-dimethyl-3-n-butyl imidazole.
8. modified polymer electrolyte according to claim 7, is characterized in that, described lithium salts is LiPF
6, LiCF
3sO
3or LiBF
4, described polymeric matrix is that polyethylene glycol oxide, described ionic liquid are 3-methyl isophthalic acid-ethyl imidazol(e) tetrafluoroborate.
9. the application of modified polymer electrolyte claimed in claim 1 in polymer Li-ion battery.
10. the application of modified polymer electrolyte claimed in claim 9 in polymer Li-ion battery, is characterized in that, described polymer Li-ion battery comprises all solid state lithium ion polymer battery and gel polymer battery.
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